Potential functions of internal rotation of the methacryloyl fluoride molecule in the ground (S0) and excited (S1) electronic states

被引:6
|
作者
Koroleva, Lidiya A. [1 ]
Abramenkov, Alexander, V [1 ]
Krasnoshchekov, Sergey, V [1 ]
Korolyova, Alexandra, V [2 ]
Bochenkova, Anastasia, V [1 ]
机构
[1] Lomonosov Moscow State Univ, Dept Chem, Leninskiye Gory 1-3, Moscow 119991, Russia
[2] Lomonosov Moscow State Univ, Dept Phys, Leninskiye Gory 1-3, Moscow 119991, Russia
关键词
Potential functions of internal rotation; s-trans-isomer; s-cis-isomer; Ground and excited electronic states; Structural parameters; PI-ASTERISK TRANSITION; UV ABSORPTION-SPECTRUM; VIBRATIONAL STRUCTURE; MICROWAVE-SPECTRUM; ACRYLOYL FLUORIDE;
D O I
10.1016/j.molstruc.2018.12.065
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The potential functions of internal rotation V(phi) (PFIR) of methacryloyl fluoride (MAF) in the ground (S-0) and excited (S-1) electronic states were reconstructed using the TORSIO program from experimental energy levels of the torsional transitions in the s-trans- and s-cis isomers. The energy levels were obtained from the analysis of the vibrational structure in the high-resolution gas-phase UV spectrum. The (S-0) and (S-1) equilibrium geometries of the s-trans- and s-cis rotational isomers of MAF as well as structural parameters for a set of points along the relaxed geometry scans, which were used to find expansion coefficients of kinematic function F(phi) in the Fourier series, were calculated using extended multiconfiguration quasi-degenerate perturbation theory, XMCQDPT2/SA(2)-CASSCF(6,5)/aug-cc-pVTZ. The ground (S-0) state calculations were also done at the MP2 level of theory. In (S-0) state, parameters V-n, barriers of internal rotation Delta H-double dagger and Delta H of MAF isomers were calculated using two theories. The calculated values of V-n, Delta H-double dagger, Delta H in (S-0) state are in good agreement with those derived from the vibrationally resolved UV spectrum of MAF in the gas phase. Within the one-dimensional model, the experimentally derived barrier heights that hinder internal rotation in MAF were found to be 2100 +/- 50 cm(-1) and 4950 +/- 250 cm(-1) in the (S-0) and (S-1) states, respectively. The parameters V-n and Delta H-double dagger in (S-1) state are determined for first time. (C) 2018 Elsevier B.V. All rights reserved.
引用
收藏
页码:228 / 234
页数:7
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